Beta-delithiated layered nickel oxide electrochemically active cathode material and a battery including said material

ABSTRACT

The invention is directed towards an electrochemically active cathode material. The electrochemically active cathode includes beta-delithiated layered nickel oxide. The beta-delithiated layered nickel oxide has an X-ray diffraction pattern. The X-ray diffraction pattern of the beta-delithiated layered nickel oxide includes a first peak from about 14.9°2θ to about 16.0°2θ; a second peak from about 21.3°2θ to about 22.7°2θ; a third peak from about 37.1°2θ to about 37.4°2θ; a fourth peak from about 43.2°2θ to about 44.0°2θ; a fifth peak from about 59.6°2θ to about 60.6°2θ; and a sixth peak from about 65.4°2θ to about 65.9°2θ.

FIELD OF THE INVENTION

The invention relates to an electrochemically active cathode materialand, more specifically, relates to a beta-delithiated layered nickeloxide electrochemically active cathode material.

BACKGROUND OF THE INVENTION

Electrochemical cells, or batteries, are commonly used as electricalenergy sources. A battery contains a negative electrode, typicallycalled the anode, and a positive electrode, typically called thecathode. The anode contains an electrochemically active anode materialthat can be oxidized. The cathode contains an electrochemically activecathode material that can be reduced. The electrochemically active anodematerial is capable of reducing the electrochemically active cathodematerial. A separator is disposed between the anode and the cathode. Thebattery components are disposed in a can, or housing, that is typicallymade from metal.

When a battery is used as an electrical energy source in an electronicdevice, electrical contact is made to the anode and the cathode,allowing electrons to flow through the device and permitting therespective oxidation and reduction reactions to occur to provideelectrical power to the electronic device. An electrolyte is in contactwith the anode, the cathode, and the separator. The electrolyte containsions that flow through the separator between the anode and cathode tomaintain charge balance throughout the battery during discharge.

There is a growing need to make batteries that are better suited topower contemporary electronic devices such as toys; remote controls;audio devices; flashlights; digital cameras and peripheral photographyequipment; electronic games; toothbrushes; radios; and clocks. To meetthis need, batteries may include higher loading of electrochemicallyactive anode and/or cathode materials to provide increased capacity andservice life. Batteries, however, also come in common sizes, such as theAA, AAA, AAAA, C, and D battery sizes, that have fixed externaldimensions and constrained internal volumes. The ability to increaseelectrochemically active material loading alone to achieve betterperforming batteries is thus limited.

The electrochemically active cathode material of the battery is anotherdesign feature that may be adjusted in order to provide increasedperformance. For example, electrochemically active material that hashigher volumetric and gravimetric capacity may result in a betterperforming battery. Similarly, electrochemically active material thathas a higher oxidation state may also result in a better performingbattery. The electrochemically active material that is selected,however, must provide an acceptable closed circuit voltage, or runningvoltage, range for the devices that the battery may power. The devicemay be damaged if the OCV or running voltages of the battery are toohigh. Conversely, the device may not function at all if the runningvoltage of the battery is too low. In addition, electrochemically activematerial, such as high oxidation state transition metal oxide, may behighly reactive. The highly reactive nature of such electrochemicallyactive material may lead to gas evolution when the electrochemicallyactive material is incorporated within a battery and is brought intocontact with the electrolyte. Any gas that is evolved may lead tostructural issues within the battery, such as continuity within thecathode, and/or leakage of electrolyte from the battery. The highoxidation state transition metal oxide may detrimentally react withother battery components, such as carbon additives, e.g., graphite;other additives, e.g., surfactant(s); and/or the separator. The highoxidation state transition metal oxide may also have a tendency toconsume electrolyte, which may lead to other structural issues withinthe battery, such as cathode swelling, and unfavorable water balancewithin the battery. Also, a battery including high oxidation statetransition metal oxide as an electrochemically active cathode materialmay, for example, exhibit instability and an elevated rate ofself-discharge when the battery is stored for a period of time.

There exists a need to provide an electrochemically active cathodematerial for a battery that address the needs discussed above. Thebeta-delithiated layered nickel oxide electrochemically active cathodematerial of the present invention addresses, inter alia, these needs.

SUMMARY OF THE INVENTION

In one embodiment, the invention is directed towards anelectrochemically active cathode material. The electrochemically activecathode includes a beta-delithiated layered nickel oxide. Thebeta-delithiated layered nickel oxide has an X-ray diffraction pattern.The X-ray diffraction pattern of the beta-delithiated layered nickeloxide includes a first peak from about 14.9°2θ to about 16.0°2θ; asecond peak from about 21.3°2θ to about 22.7°2θ; a third peak from about37.1°2θ to about 37.4°2θ; a fourth peak from about 43.2°2θ to about44.0°2θ; a fifth peak from about 59.6°2θ to about 60.6°2θ; and a sixthpeak from about 65.4°2θ to about 65.9°2θ.

In another embodiment, the invention is directed toward a battery. Thebattery includes a cathode; an anode; a separator between the anode andthe cathode; and an electrolyte. The cathode includes a conductiveadditive and an electrochemically active cathode material. Theelectrochemically active cathode material includes a beta-delithiatedlayered nickel oxide. The anode includes an electrochemically activeanode material. The electrochemically active anode material includeszinc. The beta-delithiated layered nickel oxide has an X-ray diffractionpattern. The X-ray diffraction pattern of the beta-delithiated layerednickel oxide includes a first peak from about 14.9°2θ to about 16.0°2θ;a second peak from about 21.3°2θ to about 22.7°2θ; a third peak fromabout 37.1°2θ to about 37.4°2θ; a fourth peak from about 43.2°2θ toabout 44.0°2θ; a fifth peak from about 59.6°2θ to about 60.6°2θ; and asixth peak from about 65.4°2θ to about 65.9°2θ.

BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims particularly pointing outand distinctly claiming the subject matter, which is regarded as formingthe present invention, it is believed that the invention will be betterunderstood from the following description taken in conjunction with theaccompanying drawings.

FIG. 1 is a cross-section of a primary alkaline battery including anembodiment of the beta-delithiated layered nickel oxideelectrochemically active cathode material of the present invention.

FIG. 2 includes a powder X-ray diffraction pattern for an embodiment ofthe beta delithiated layered nickel oxide electrochemically activecathode material of the present invention along with powder X-raydiffraction patterns for other materials.

FIG. 3 is a perspective view of a primary alkaline battery of thepresent invention including a voltage indicator.

DETAILED DESCRIPTION OF THE INVENTION

Electrochemical cells, or batteries, may be primary or secondary.Primary batteries are meant to be discharged, e.g., to exhaustion, onlyonce and then discarded. Primary batteries are described, for example,in David Linden, Handbook of Batteries (4^(th) ed. 2011). Secondarybatteries are intended to be recharged. Secondary batteries may bedischarged and recharged many times, e.g., more than fifty times, ahundred times, or more. Secondary batteries are described, for example,in David Linden, Handbook of Batteries (4^(th) ed. 2011). Accordingly,batteries may include various electrochemical couples and electrolytecombinations. Although the description and examples provided herein aregenerally directed towards primary alkaline electrochemical cells, orbatteries, it should be appreciated that the invention applies to bothprimary and secondary batteries of aqueous, nonaqueous, ionic liquid,and solid state systems. Primary and secondary batteries of theaforementioned systems are thus within the scope of this application andthe invention is not limited to any particular embodiment.

Referring to FIG. 1, there is shown a primary alkaline electrochemicalcell, or battery, 10 including a cathode 12, an anode 14, a separator16, and a housing 18. Battery 10 also includes current collector 20,seal 22, and an end cap 24. The end cap 24 serves as the negativeterminal of the battery 10. A positive pip 26 is at the opposite end ofthe battery 10 from the end cap 24. The positive pip 26 may serve as thepositive terminal of the battery 10. An electrolytic solution isdispersed throughout the battery 10. The cathode 12, anode 14, separator16, electrolyte, current collector 20, and seal 22 are contained withinthe housing 18. Battery 10 can be, for example, a AA, AAA, AAAA, C, or Dalkaline battery.

The housing 18 can be of any conventional type of housing commonly usedin primary alkaline batteries and can be made of any suitable basematerial, for example cold-rolled steel or nickel-plated cold-rolledsteel. The housing 18 may have a cylindrical shape. The housing 18 maybe of any other suitable, non-cylindrical shape. The housing 18, forexample, may have a shape comprising at least two parallel plates, suchas a rectangular, square, or prismatic shape. The housing 18 may be, forexample, deep-drawn from a sheet of the base material, such ascold-rolled steel or nickel-plated steel. The housing 18 may be, forexample, drawn into a cylindrical shape. The housing 18 may have atleast one open end. The housing 18 may have a closed end and an open endwith a sidewall therebetween. The interior surface of the sidewall ofthe housing 18 may be treated with a material that provides a lowelectrical-contact resistance between the interior surface of thesidewall of the housing 18 and an electrode, such as the cathode 12. Theinterior surface of the sidewall of the housing 18 may be plated, e.g.,with nickel, cobalt, and/or painted with a carbon-loaded paint todecrease contact resistance between, for example, the internal surfaceof the sidewall of the housing 18 and the cathode 12.

The cathode 12 includes at least one electrochemically active cathodematerial. The electrochemically active cathode material may be abeta-delithiated layered nickel oxide. The beta-delithiated layerednickel oxide may have the general chemical formulaLi_(x)A_(y)Ni_(1+a−z)M_(z)O₂.nH₂O where x is from about 0.02 to about0.20; y is from about 0.03 to about 0.20; a is from about 0 to about0.2; z is from about 0 to about 0.2; n is from about 0 to about 1; Acomprises an alkali metal; and M comprises an alkaline earth metal, atransition metal, a non-transition metal, and any combination thereof.

Elements from Group 1A of the Periodic Table of Elements are commonlyreferred to as alkali metals. The alkali metal may include an element,or any combination of elements, from Group 1A of the Periodic Table ofElements. The alkali metal may comprise, for example, potassium (K),rubidium (Rb), cesium (Cs), and any combination thereof.

Elements from Group IIA of the Periodic Table of Elements are typicallyreferred to as alkaline earth metals. The alkaline earth metal maycomprise an element, or any combination of elements, from Group IIA ofthe Periodic Table of Elements. The alkaline earth metal may comprise,for example, magnesium (Mg).

Elements from Groups IB-VIIIB of the Periodic Table of Elements aretypically referred to as transition metals. The transition metal maycomprise an element, or any combination of elements, from GroupsIB-VIIIB of the Period Table of Elements. The transition metal maycomprise, for example, cobalt (Co), manganese (Mn), zinc (Zn), yttrium(Y), titanium (Ti), and any combination thereof.

The non-transition metal may comprise, for example, aluminum (Al),gallium (Ga), germanium (Ge), indium (In), tin (Sn), and any combinationthereof.

The alkali metal may be, for example, potassium (K). The chemicalformula of the beta-delithiated layered nickel oxide may be, forexample, Li_(x)K_(y)N_(1+a-z)M_(z)O₂.nH₂O where x is from about 0.02 toabout 0.20; y is from about 0.03 to about 0.20; a is from about 0 toabout 0.2; z is from about 0 to about 0.2; n is from about 0 to about 1.The chemical formula of the beta-delithiated layered nickel oxide maybe, for example, Li_(0.11)K_(0.11)NiO₂.0.5H₂O orLi_(0.06)K_(0.12)NiO₂.0.53H₂O.

The alkaline earth metal may be, for example, magnesium (Mg). Thechemical formula of the beta-delithiated layered nickel oxide may be,for example, Li_(x)K_(y)Ni_(1+a-z)Mg_(z)O₂.nH₂O wherein x is from about0.02 to about 0.2; y is from about 0.03 to about 0.2; a is from about 0to about 0.2; z is from about 0 to about 0.2; and n is from about 0 toabout 1. The chemical formula of the beta-delithiated layered nickeloxide may be, for example,Li_(0.15)K_(0.10)Ni_(1.05)Mg_(0.04)O₂.0.24H₂O.

The transition metal may be, for example, cobalt (Co). The chemicalformula of the beta-delithiated layered nickel oxide may be, forexample, Li_(x)K_(y)Ni_(1+a-z)Co_(z)O₂.nH₂O wherein x is from about 0.02to about 0.2; y is from about 0.03 to about 0.2; a is from about 0 toabout 0.2; z is from about 0 to about 0.2; and n is from about 0 toabout 1. The chemical formula of the beta-delithiated layered nickeloxide may be, for example, Li_(0.04)K_(0.11)Ni_(0.97)Co_(0.03)O₂.nH₂O.

The non-transition metal may be, for example, aluminum (Al). Thechemical formula of the beta-delithiated layered nickel oxide may be,for example, Li_(x)K_(y)Ni_(1+a) _(_) _(z)Al_(z)O₂.nH₂O wherein x isfrom about 0.02 to about 0.2; y is from about 0.03 to about 0.2; a isfrom about 0 to about 0.2; z is from about 0 to about 0.2; and n is fromabout 0 to about 1. The chemical formula of the beta-delithiated layerednickel oxide may be, for example,Li_(0.12)K_(0.09)Ni_(1.08)Al_(0.02)O₂.0.18H₂O.

The content of the alkali metal(s), alkaline earth metal(s), transitionmetal(s), and/or non-transition metal(s) within the beta-delithiatedlayered nickel oxide may be determined by any acceptable method known inthe art. For example, the content of the alkali metal(s) and transitionmetal(s) within the beta-delithiated layered nickel oxide may bedetermined by inductively coupled plasma atomic emission (ICP-AE)spectroscopy and/or atomic absorption (AA) spectroscopy. ICP-AE and/orAA analyses may be completed, for example, using standard methods asdescribed, for example, by J. R. Dean, Practical Inductively CoupledPlasma Spectroscopy, pp. 65-87 (2005) and B. Welz and M. B. Sperling,Atomic Absorption Spectrometry, pp. 221-294 (3^(rd) ed. 1999). An Ultima2 ICP spectrometer, available from HORIBA Scientific (Kyoto, Japan), maybe used to complete ICP-AE analysis on a sample material, such as abeta-delithiated layered nickel oxide. ICP-AE analysis of thebeta-delithiated layered nickel oxide can be performed at varyingwavelengths depending upon the elements contained within thebeta-delithiated layered nickel oxide.

The water content within the beta-delithiated layered nickel oxide maybe determined by any acceptable method known in the art. For example,the water content within the beta-delithiated layered nickel oxide maybe determined by thermogravimetric analysis (TGA). TGA determines, forexample, the absorbed and adsorbed water of the sample material; thewater content within the crystal lattice of the sample material; and thetotal water content within the sample material by measuring the changein weight of the sample as a function of increasing temperature. TGA isdescribed, for example, by R. F. Speyer, Thermal Analysis of Materials(1994). A Q5000 analyzer, available from TA Instruments (Newcastle,Del., USA), may be used to complete TGA on a sample material, such as abeta-delithiated layered nickel oxide.

Powder X-ray diffraction (XRD) is an analytical technique that is usedto characterize the crystal lattice structure of a sample material, suchas a crystalline powder. XRD analysis of a crystalline sample materialwill result in a characteristic diffraction pattern consisting of peaksof varying intensities, widths, and diffraction angles (peak positions)corresponding to diffraction planes in the crystal structure of thesample material. XRD patterns can be measured with an X-raydiffractometer using CuK_(α) radiation by standard methods as isdescribed, for example, by B. D. Cullity and S. R. Stock, Elements ofX-ray Diffraction (3^(rd) ed. 2001). A D-8 Advance X-ray diffractometer,available from Bruker Corporation (Madison, Wis., USA), may be used tocomplete powder XRD analysis on a sample material, such as abeta-delithiated layered nickel oxide.

The unit cell parameters, such as unit cell lengths and angles, of thesample material can be determined, for example, by Rietveld refinementof the XRD pattern. Rietveld refinement is described, for example, by H.M. Rietveld, A Profile Refinement Method for Nuclear and MagneticStructures, 2 J. Appl. Cryst., pp. 65-71 (1969).

The crystallite size of the sample material can be determined by peakbroadening of the XRD pattern of a sample material that contains asilicon (Si) standard. Peak broadening analysis may be completed, forexample, by the single-peak Scherrer method or the Warren-Averbachmethod as is discussed, for example, by H. P. Klug and L. E. AlexanderX-ray Diffraction Procedures for Polycrystalline and AmorphousMaterials, pp. 618-694 (1974). The Warren-Averbach method may also beused to determine the residual strain and stress of the sample material.

The full width at half maximum (FWHM) can be used to characterize therelative sharpness, or broadness, of the lines in the diffractionpattern of the sample material. The FWHM can be determined by measuringthe intensity of a peak; dividing the measured intensity by two tocalculate half intensity (half height); and measuring the width in 2θ ofthe peak at the calculated half height.

The normalized intensity can be used, along with peak position, tocompare the relative efficiency of diffraction associated with theparticular diffraction planes within the crystal lattice of the samplematerial. The normalized intensity may be calculated for peaks withinthe same XRD pattern. All peaks of the XRD pattern may be normalized tothe peak having the highest intensity (the reference peak).Normalization, which is reported in percent, occurs by dividing theintensity of the peak being normalized by the intensity of the referencepeak and multiplying by 100. For example, the reference peak may have anintensity of 425 and the peak being normalized may have an intensity of106. The normalized intensity of the peak is 25%, e.g., [(106/425)·100].The reference peak will have a normalized intensity of 100%.

The resulting XRD pattern may be compared with known XRD patterns. Thecomparative XRD patterns may be generated from known sample materials.In addition, the resulting XRD pattern may be compared with known XRDpatterns within, for example, the Powder Diffraction File (PDF)database, available from International Centre for Diffraction Data(Newton Square, Pa., USA), or the Inorganic Crystal Structure Database(ICSD), available from FIZ Karlsruhe (Eggenstein-Leopoldshafen,Germany). The comparison to known sample materials or PDF determines ifthe resulting XRD pattern of the sample material is distinct, similar,or equivalent to known XRD patterns of materials. Known XRD patternswithin the PDF database for comparison to, for example, beta-delithiatedlayered nickel oxide include PDF #00-06-0141 for beta-nickeloxyhydroxide; PDF #00-00675 for gamma-nickel oxyhydroxide; PDF#00-059-0463 for nickel oxide; PDF #00-059-0463 for beta-nickelhydroxide; and PDF #00-036-0791 for potassium hydroxide.

The beta-delithiated layered nickel oxide may have a characteristic XRDpattern. The XRD pattern may include several peaks, or combination ofpeaks, that are indicative of the beta-delithiated layered nickel oxide.The XRD pattern may include characteristic FWHM values for the severalpeaks of the beta-delithiated layered nickel oxide. The XRD pattern mayalso include characteristic normalized intensities for the several peaksof the beta-delithiated layered nickel oxide.

The XRD pattern of the beta-delithiated layered nickel oxide may includea first peak. The first peak may have a peak position on the XRD patternof from about 14.9°2θ to about 16.0°2θ. The first peak may be, forexample, at about 15.4°2θ. The XRD pattern of the beta-delithiatedlayered nickel oxide may include a second peak. The second peak may havea peak position on the XRD pattern of from about 21.3°2θ to about22.7°2θ. The second peak may be, for example, at about 22.1°2θ. The XRDpattern of the beta-delithiated layered nickel oxide may include a thirdpeak. The third peak may have a peak position on the XRD pattern of fromabout 37.1°2θ to about 37.4°2θ. The third peak may be, for example, atabout 37.3°2θ. The XRD pattern of the beta-delithiated layered nickeloxide may include a fourth peak. The fourth peak may have a peakposition on the XRD pattern of from about 43.2°2θ to about 44.0°2θ. Thefourth peak may be, for example, at about 43.6°2θ. The XRD pattern ofthe beta-delithiated layered nickel oxide may include a fifth peak. Thefifth peak may have a peak position on the XRD pattern of from about59.6°2θ to about 60.6°2θ. The fifth peak may be, for example, at about60.1°2θ. The XRD pattern of the beta-delithiated layered nickel oxidemay include a sixth peak. The sixth peak may have a peak position on theXRD pattern of from about 65.4°2θ to about 65.9°2θ. The sixth peak maybe, for example, at about 65.7°2θ. The XRD pattern of thebeta-delithiated layered nickel oxide may include a seventh peak. Theseventh peak may have a peak position on the XRD pattern of from about10.8°2θ to about 12.0°2θ. The seventh peak may be, for example, at about11.2°2θ. The XRD pattern of the beta-delithiated layered nickel oxidemay include an eighth peak. The eighth peak may have a peak position onthe XRD pattern of from about 47.2°2θ to about 47.4°2θ. The eighth peakmay be, for example, at about 47.3°2θ. The XRD pattern of thebeta-delithiated layered nickel oxide may include a ninth peak. Theninth peak may have a peak position on the XRD pattern of from about48.1°2θ to about 48.6°2θ. The ninth peak may be, for example, at about48.3°2θ.

The first peak of the XRD pattern of the beta-delithiated layered nickeloxide may have a FWHM (FWHM). The FWHM of the first peak may be fromabout 1.01 to about 2.09. The FWHM of the first peak may be, forexample, about 1.37. The second peak of the XRD pattern of thebeta-delithiated layered nickel oxide may have a FWHM. The FWHM of thesecond peak may be from about 0.86 to about 1.95. The FWHM of the secondpeak may be, for example, about 1.37. The third peak of the XRD patternof the beta-delithiated layered nickel oxide may have a FWHM. The FWHMof the third peak may be from about 0.23 to about 0.41. The FWHM of thethird peak may be, for example, about 0.28. The fourth peak of the XRDpattern of the beta-delithiated layered nickel oxide may have a FWHM.The FWHM of the fourth peak may be from about 0.40 to about 0.75. TheFWHM of the fourth peak may be, for example, about 0.60. The fifth peakof the XRD pattern of the beta-delithiated layered nickel oxide may havea FWHM. The FWHM of the fifth peak may be from about 0.57 to about 1.45.The FWHM of the fifth peak may be, for example, about 0.92. The sixthpeak of the XRD pattern of the beta-delithiated layered nickel oxide mayhave a FWHM. The FWHM of the sixth peak may be from about 0.27 to about0.53. The FWHM of the sixth peak may be, for example, about 0.36. Theseventh peak of the XRD pattern of the beta-delithiated layered nickeloxide may have a FWHM. The FWHM of the seventh peak may be from about0.56 to about 1.73. The FWHM of the seventh peak may be, for example,about 1.13. The eighth peak of the XRD pattern of the beta-delithiatedlayered nickel oxide may have a FWHM. The FWHM of the eighth peak may befrom about 0.08 to about 0.21. The FWHM of the eighth peak may be, forexample, about 0.15. The ninth peak of the XRD pattern of thebeta-delithiated layered nickel oxide may have a FWHM. The FWHM of theninth peak may be from about 0.33 to about 0.58. The FWHM of the ninthpeak may be, for example, about 0.45.

The peaks of the XRD pattern of the beta-delithiated layered nickeloxide may be normalized. The peaks of the XRD pattern may be normalized,for example, to the third peak of the XRD pattern. The normalizedintensity of the first peak of the XRD pattern may be from about 13% toabout 37%. The normalized intensity of the first peak of the XRD patternmay be, for example, about 24%. The normalized intensity of the secondpeak of the XRD pattern may be from about 6% to about 16%. Thenormalized intensity of the second peak of the XRD pattern may be, forexample, about 10%. The normalized intensity of the third peak of theXRD pattern may be, for example, 100%. The normalized intensity of thefourth peak of the XRD pattern may be from about 45% to about 73%. Thenormalized intensity of the fourth peak of the XRD pattern may be, forexample, about 58%. The normalized intensity of the fifth peak of theXRD pattern may be from about 7% to about 17%. The normalized intensityof the fifth peak of the XRD pattern may be, for example, about 11%. Thenormalized intensity of the sixth peak of the XRD pattern may be fromabout 41% to about 61%. The normalized intensity of the sixth peak ofthe XRD pattern may be, for example, about 48%. The normalized intensityof the seventh peak of the XRD pattern may be from about 2% to about18%. The normalized intensity of the seventh peak of the XRD pattern maybe, for example, about 6%. The normalized intensity of the eighth peakof the XRD pattern may be from about 8% to about 20%. The normalizedintensity of the eighth peak of the XRD pattern may be, for example,about 10%. The normalized intensity of the ninth peak of the XRD patternmay be from about 6% to about 20%. The normalized intensity of the ninthpeak of the XRD pattern may be, for example, about 12%.

An electrochemically active material, such as a beta-delithiated layerednickel oxide, may produce gas, for example oxygen gas, when the materialis placed in contact with an aqueous electrolyte. The rate of gasgeneration when an electrochemically active material is placed incontact with an electrolyte may be observed qualitatively and may bedetermined quantitatively.

The qualitative rate of gas generation rate (GER) of anelectrochemically active material may be determined through visualobservation. For example, a quantity of electrochemically activematerial, such as beta-delithiated layered nickel oxide, may be placedwithin a container, such as a Petri dish. A quantity of electrolyte,such as a nine normal (9N) aqueous solution of potassium hydroxide, maythen be added to the Petri dish that includes the electrochemicallyactive material. Gas bubbles may begin to form when the electrolytecontacts the electrochemically active material. The formation of gasbubbles may be, for example, slow, rapid, and, in some instances,violent. The visual formation of gas bubbles for one electrochemicallyactive material may be qualitatively compared with one or more otherelectrochemically active materials. The beta-delithiated layered nickeloxide may exhibit a lower qualitative GER when compared to otherelectrochemically active materials having high oxidation states, such asa high oxidation state transition metal oxide, e.g., alpha-delithiatednickel oxide.

The quantitative rate of gas generation may be determined by a gasevolution rate (GER) monitor. For example, a quantity ofelectrochemically active material, such as beta-delithiated layerednickel oxide, may be mixed with a quantity of electrolyte, such as anine normal (9N) aqueous solution of potassium hydroxide. The mixturemay be placed within a container that may be sealed closed, such as aglass jar. The glass jar may then be sealed and may be stored at roomconditions or at an elevated temperature, such as within an oven. Apressure sensor may be attached to, for example, the cap of the glassjar. The pressure sensor may monitor the change in gas pressure withinthe glass jar resulting from any gas that may be generated when theelectrolyte contacts the electrochemically active material. A Series 27Apressure sensor, available from Valcom S.r.l. (Milan, Italy), may be asuitable pressure sensor. A data acquisition unit may be attached to thepressure sensor to record the change in gas pressure within the glassjar over time. A 34970A data acquisition/data logger switch unit,available from Agilent Technologies, Inc. (Santa Clara, Calif., USA), isa suitable data acquisition unit. The beta-delithiated layered nickeloxide may exhibit a lower quantitative GER when compared to otherelectrochemically active materials having high oxidation states, such asa high oxidation state transition metal oxide, e.g., alpha-delithiatednickel oxide.

The stability of an electrochemically active material, such as abeta-delithiated layered nickel oxide, may be evaluated using isothermalmicrocalorimetry (IMC). IMC measures and records the heat flow to orfrom a sample material resulting from a dynamic chemical and/or physicalprocess over time. IMC also measures and records the cumulative amountof heat absorbed or generated by the chemical and/or physical process.IMC is described, for example, in M. E. Brown, Handbook of ThermalAnalysis and Calorimetry Volume 1 Principles and Practice (1998). IMCmeasurements may be made and recorded when a quantity ofelectrochemically active material, such as a beta-delithiated layerednickel oxide, is placed into a sample holder, such as a plastic sampleholder, along with an electrolyte, such as a nine normal (9N) aqueouspotassium hydroxide electrolyte. The sample holder may be sealed andplaced into a temperature-controlled bath, for example, at about 40° C.The reaction between, for example, the beta-delithiated layered nickeloxide and the electrolyte may be exothermic. The heat generation fromthe exothermic reaction process may be measured and recorded using, forexample, a TAM III isothermal microcalorimeter, available from TAInstruments (Newcastle, Del., USA). The beta-delithiated layered nickeloxide may exhibit improved stability, e.g., lower heat generation, whencompared to other electrochemically active materials having highoxidation states, such as a high oxidation state transition metal oxide,e.g., alpha-delithiated nickel oxide.

The cathode 12 may also include at least one or more additionalelectrochemically active cathode materials. The additionalelectrochemically active cathode material may include manganese oxide,manganese dioxide, electrolytic manganese dioxide (EMD), chemicalmanganese dioxide (CMD), high power electrolytic manganese dioxide (HPEMD), lambda manganese dioxide, gamma manganese dioxide, beta manganesedioxide, and mixtures thereof. Other electrochemically active cathodematerials include, but are not limited to, silver oxide; nickel oxide;nickel oxyhydroxide; copper oxide; copper salts, such as copper iodate;bismuth oxide; high-valence nickel compound; oxygen; and mixturesthereof. The nickel oxide can include nickel hydroxide, nickeloxyhydroxide, cobalt oxyhydroxide-coated nickel oxyhydroxide,alpha-delithiated layered nickel oxide, and combinations thereof. Thenickel hydroxide or oxyhydroxide can include beta-nickel oxyhydroxide,gamma-nickel oxyhydroxide, and/or intergrowths of beta-nickeloxyhydroxide and/or gamma-nickel oxyhydroxide. The cobaltoxyhydroxide-coated nickel oxyhydroxide can include cobaltoxyhydroxide-coated beta-nickel oxyhydroxide, cobalt oxyhydroxide-coatedgamma-nickel oxyhydroxide, and/or cobalt oxyhydroxide-coatedintergrowths of beta-nickel oxyhydroxide and gamma-nickel oxyhydroxide.

The cathode 12 may include a conductive additive, such as carbon, and abinder. The cathode 12 may also include other additives. The carbon mayincrease the conductivity of the cathode 12 by facilitating electronflow within the solid structure of the cathode 12. The carbon may begraphite, such as expanded graphite and natural graphite; graphene,single-walled nanotubes, multi-walled nanotubes, carbon fibers; carbonnanofibers; and mixtures thereof. It is preferred that the amount ofcarbon in the cathode is relatively low, e.g., less than about 12%, lessthan about 10%, less than about 9%, less than about 8%, less than about6%, less than about 3.75%, or even less than about 3.5%, for examplefrom about 2.0% to about 3.5%. The lower carbon level enables inclusionof a higher loading of electrochemically active cathode material withinthe cathode 12 without increasing the volume of the cathode 12 orreducing the void volume (which must be maintained at or above a certainlevel to prevent internal pressure from rising too high as gas isgenerated within the cell) within the battery 10. Suitable graphite foruse within a battery may be, for example, BNB-90 and/or BNC-30,available from TIMCAL Carbon & Graphite (Bodio, Switzerland).

It is generally preferred that the cathode be substantially free ofnon-expanded graphite. While non-expanded graphite particles providelubricity to the cathode pellet forming process, this type of graphiteis significantly less conductive than expanded graphite, and thus it isnecessary to use more non-expanded graphite in order to obtain the samecathode conductivity of a cathode containing expanded graphite. Thecathode 12 may include low levels of non-expanded graphite. Theinclusion of non-expanded graphite, however, may compromise thereduction in graphite concentration that can be obtained whilemaintaining an adequate level of cathode conductivity due to the lowerconductivity of non-expanded graphite.

Examples of optional binders that may be used in the cathode 12 includepolyethylene, polyacrylic acid, or a fluorocarbon resin, such as PVDF orPTFE. An optional binder for use within a battery may be, for example,COATHYLENE HA-1681, available from E. I. du Pont de Nemours and Company(Wilmington, Del., USA). Examples of other cathode additives aredescribed in, for example, U.S. Pat. Nos. 5,698,315, 5,919,598,5,997,775 and 7,351,499.

The amount of electrochemically active cathode material within thecathode 12 may be referred to as the cathode loading. The loading of thecathode 12 may vary depending upon the electrochemically active cathodematerial used within, and the size of, the battery 10. For example, a AAbattery with a beta-delithiated layered nickel oxide may have a cathodeloading of at least about 6 grams of beta-delithiated layered nickeloxide. The cathode loading may be, for example, at least about 7 gramsof beta-delithiated layered nickel oxide. The cathode loading may be,for example, between about 7.2 grams to about 11.5 grams ofbeta-delithiated layered nickel oxide. The cathode loading may be fromabout 8 grams to about 10 grams of beta-delithiated layered nickeloxide. The cathode loading may be from about 8.5 grams to about 9.5grams of beta-delithiated layered nickel oxide. The cathode loading maybe from about 9.5 grams to about 11.5 grams of beta-delithiated layerednickel oxide. The cathode loading may be from about 10.4 grams to about11.5 grams of beta-delithiated layered nickel oxide. For a AAA battery,the cathode loading may be at least about 1.4 grams of beta-delithiatedlayered nickel oxide. The cathode loading may be from about 1.4 grams toabout 2.3 grams of beta-delithiated layered nickel oxide. The cathodeloading may be from about 1.6 grams to about 2.1 grams ofbeta-delithiated layered nickel oxide. The cathode loading may be fromabout 1.7 grams to about 1.9 grams of beta-delithiated layered nickeloxide. For a AAAA battery, the cathode loading may be from about 0.7grams to about 1.2 grams of beta-delithiated layered nickel oxide. For aC battery, the cathode loading may be from about 27.0 grams to about40.0 grams, for example about 33.5 grams, of beta-delithiated layerednickel oxide. For a D battery, the cathode loading may be from about60.0 grams to about 84.0 grams, for example about 72.0 grams, ofbeta-delithiated layered nickel oxide.

The cathode components, such as active cathode material(s), carbonparticles, binder, and any other additives, may be combined with aliquid, such as an aqueous potassium hydroxide electrolyte, blended, andpressed into pellets for use in the assembly of the battery 10. Foroptimal cathode pellet processing, it is generally preferred that thecathode pellet have a moisture level in the range of about 2.5% to about5%, more preferably about 2.8% to about 4.6%. The pellets, after beingplaced within the housing 18 during the assembly of the battery 10, aretypically re-compacted to form a uniform cathode assembly within thehousing 18.

The cathode 12 will have a porosity that may be calculated at the timeof cathode manufacture. The porosity of the cathode 12 may be from about20% to about 40%, between about 22% and about 35%, and, for example,about 26%. The porosity of the cathode 12 may be calculated at the timeof manufacturing, for example after cathode pellet processing, since theporosity of the cathode 12 within the battery 10 may change over timedue to, inter alia, cathode swelling associated with electrolyte wettingof the cathode and discharge of the battery 10. The porosity of thecathode 12 may be calculated as follows. The true density of each solidcathode component may be taken from a reference book, for exampleLange's Handbook of Chemistry (16^(th) ed. 2005). The solids weight ofeach of the cathode components are defined by the battery design. Thesolids weight of each cathode component may be divided by the truedensity of each cathode component to determine the cathode solidsvolume. The volume occupied by the cathode 12 within the battery 10 isdefined, again, by the battery design. The volume occupied by thecathode 12 may be calculated by a computer-aided design (CAD) program.The porosity may be determined by the following formula:

Cathode Porosity=[1−(cathode solids volume÷cathode volume)]×100

For example, the cathode 12 of a AA battery may include about 9.0 gramsof alpha-delithiated layered nickel oxide and about 0.90 grams ofgraphite (BNC-30) as solids within the cathode 12. The true densities ofthe alpha-delithiated layered nickel oxide and graphite may be,respectively, about 4.9 g/cm³ and about 2.15 g/cm³. Dividing the weightof the solids by the respective true densities yields a volume occupiedby the alpha-delithiated layered nickel oxide of about 1.8 cm³ and avolume occupied by the graphite of about 0.42 cm³. The total solidsvolume is about 2.2 cm³. The battery designer may select the volumeoccupied by the cathode 12 to be about 3.06 cm³. Calculating the cathodeporosity per the equation above [1−(2.2 cm³÷3.06 cm³)] yields a cathodeporosity of about 0.28, or 28%.

The anode 14 can be formed of at least one electrochemically activeanode material, a gelling agent, and minor amounts of additives, such asorganic and/or inorganic gassing inhibitor. The electrochemically activeanode material may include zinc; zinc oxide; zinc hydroxide; cadmium;iron; metal hydride, such as AB₅(H), AB₂(H), and A₂B₇(H); alloysthereof; and mixtures thereof.

The amount of electrochemically active anode material within the anode14 may be referred to as the anode loading. The loading of the anode 14may vary depending upon the electrochemically active anode material usedwithin, and the size of, the battery. For example, a AA battery with azinc electrochemically active anode material may have an anode loadingof at least about 3.3 grams of zinc. The anode loading may be, forexample, at least about 3.5 grams, about 3.7 grams, about 3.9 grams,about 4.1 grams, about 4.3 grams, or about 4.5 grams of zinc. The anodeloading may be from about 4.0 grams to about 5.2 grams of zinc. Theanode loading may be from about 4.2 grams to about 5.0 grams of zinc.For example, a AAA battery with a zinc electrochemically active anodematerial may have an anode loading of at least about 1.8 grams of zinc.For example, the anode loading may be from about 1.8 grams to about 2.2grams of zinc. The anode loading may be, for example, from about 1.9grams to about 2.1 grams of zinc. For example, a AAAA battery with azinc electrochemically active anode material may have an anode loadingof at least about 0.6 grams of zinc. For example, the anode loading maybe from about 0.7 grams to about 1.1 grams of zinc. For example, a Cbattery with a zinc electrochemically active anode material may have ananode loading of at least about 9.5 grams of zinc. For example, theanode loading may be from about 10.0 grams to about 19.0 grams of zinc.For example, a D battery with a zinc electrochemically active anodematerial may have an anode loading of at least about 30.0 grams of zinc.For example, the anode loading may be from about 30.0 grams to about45.0 grams of zinc. The anode loading may be, for example, from about33.0 grams to about 39.5 grams of zinc.

Examples of a gelling agent that may be used include a polyacrylic acid;a polyacrylic acid cross-linked with polyalkenyl ether of divinylglycol; a grafted starch material; a salt of a polyacrylic acid; acarboxymethylcellulose; a salt of a carboxymethylcellulose (e.g., sodiumcarboxymethylcellulose); or combinations thereof. The anode 14 mayinclude a gassing inhibitor that may include an inorganic material, suchas bismuth, tin, or indium. Alternatively, the gassing inhibitor caninclude an organic compound, such as a phosphate ester, an ionicsurfactant or a nonionic surfactant.

The electrolyte may be dispersed throughout the cathode 12, the anode14, and the separator 16. The electrolyte comprises an ionicallyconductive component in an aqueous solution. The ionically conductivecomponent may be a hydroxide. The hydroxide may be, for example,potassium hydroxide, cesium hydroxide, and mixtures thereof. Theconcentration of the ionically conductive component may be selecteddepending on the battery design and its desired performance. An aqueousalkaline electrolyte may include a hydroxide, as the ionicallyconductive component, in a solution with water. The concentration of thehydroxide within the electrolyte may be from about 0.20 to about 0.40,or from about 20% to about 40%, on a weight basis of the totalelectrolyte within the battery 10. For example, the hydroxideconcentration of the electrolyte may be from about 0.25 to about 0.32,or from about 25% to about 32%, on a weight basis of the totalelectrolyte within the battery 10. The aqueous alkaline electrolyte mayalso include zinc oxide (ZnO). The ZnO may serve to suppress zinccorrosion within the anode. The concentration of ZnO included within theelectrolyte may be less than about 5% by weight of the total electrolytewithin the battery 10. The ZnO concentration, for example, may be fromabout 1% by weight to about 3% by weight of the total electrolyte withinthe battery 10.

The total weight of the aqueous alkaline electrolyte within a AAalkaline battery, for example, may be from about 3.0 grams to about 4.4grams. The total weight of the electrolyte within a AA batterypreferably may be, for example, from about 3.3 grams to about 3.8 grams.The total weight of the electrolyte within a AA battery may be, forexample, from about 3.4 grams to about 3.65 grams. The total weight ofthe aqueous alkaline electrolyte within a AAA alkaline battery, forexample, may be from about 1.0 grams to about 2.0 grams. The totalweight of the electrolyte within a AAA battery may be, for example, fromabout 1.2 grams to about 1.8 grams. The total weight of the electrolytewithin a AAA battery may be, for example, from about 1.4 grams to about1.6 grams. The total weight of the electrolyte within a AAAA battery maybe from about 0.68 grams to about 0.78 grams, for example, from about0.70 grams to about 0.75 grams. The total weight of the electrolytewithin a C battery may be from about 12.3 grams to about 14.1 grams, forexample, from about 12.6 grams to about 13.6 grams. The total weight ofthe electrolyte within a D battery may be from about 26.5 grams to about30.6 grams, for example, from about 27.3 grams to about 29.5 grams.

The separator 16 comprises a material that is wettable or wetted by theelectrolyte. A material is said to be wetted by a liquid when thecontact angle between the liquid and the surface of the material is lessthan 90° or when the liquid tends to spread spontaneously across thesurface of the material; both conditions normally coexist. The separator16 may comprise a single layer, or multiple layers, of woven or nonwovenpaper or fabric. The separator 16 may include a layer of, for example,cellophane combined with a layer of non-woven material. The separator 16also can include an additional layer of non-woven material. Theseparator 16 may also be formed in situ within the battery 10. U.S. Pat.No. 6,514,637, for example, discloses such separator materials, andpotentially suitable methods of their application. The separatormaterial may be thin. The separator 16, for example, may have a drymaterial thickness of less than 250 micrometers (microns). The separator16 may have a dry material thickness from about 50 microns to about 175microns. The separator 16 may have a dry material thickness from about70 microns to about 160 microns. The separator 16 may have a basisweight of about 40 g/m² or less. The separator 16 may have a basisweight from about 15 g/m² to about 40 g/m². The separator 16 may have abasis weight from from about 20 g/m² to about 30 g/m². The separator 16may have an air permeability value. The separator 16 may have an airpermeability value as defined in International Organization forStandardization (ISO) Standard 2965. The air permeability value of theseparator 16 may be from about 2000 cm³/cm²·min @ 1 kPa to about 5000cm³/cm²·min @ 1 kPa. The air permeability value of the separator 16 maybe from about 3000 cm³/cm²·min @ 1 kPa to about 4000 cm³/cm²·min @ 1kPa. The air permeability value of the separator 16 may be from about3500 cm³/cm²·min @ 1 kPa to about 3800 cm³/cm²·min @ 1 kPa.

The current collector 20 may be made into any suitable shape for theparticular battery design by any known methods within the art. Thecurrent collector 20 may have, for example, a nail-like shape. Thecurrent collector 20 may have a columnar body and a head located at oneend of the columnar body. The current collector 20 may be made of metal,e.g., zinc, copper, brass, silver, or any other suitable material. Thecurrent collector 20 may be optionally plated with tin, zinc, bismuth,indium, or another suitable material presenting a low electrical-contactresistance between the current collector 20 and, for example, the anode14. The plating material may also exhibit an ability to suppress gasformation when the current collector 20 is contacted by the anode 14.

The seal 22 may be prepared by injection molding a polymer, such aspolyamide, polypropylene, polyetherurethane, or the like; a polymercomposite; and mixtures thereof into a shape with predetermineddimensions. The seal 22 may be made from, for example, Nylon 6,6; Nylon6,10; Nylon 6,12; Nylon 11; polypropylene; polyetherurethane;co-polymers; composites; and mixtures thereof. Exemplary injectionmolding methods include both the cold runner method and the hot runnermethod. The seal 22 may contain other known functional materials such asa plasticizer, a crystalline nucleating agent, an antioxidant, a moldrelease agent, a lubricant, and an antistatic agent. The seal 22 mayalso be coated with a sealant. The seal 22 may be moisturized prior touse within the battery 10. The seal 22, for example, may have a moisturecontent of from about 1.0 weight percent to about 9.0 weight percentdepending upon the seal material. The current collector 20 may beinserted into and through the seal 22.

The end cap 24 may be formed in any shape sufficient to close therespective battery. The end cap 24 may have, for example, a cylindricalor prismatic shape. The end cap 24 may be formed by pressing a materialinto the desired shape with suitable dimensions. The end cap 24 may bemade from any suitable material that will conduct electrons during thedischarge of the battery 10. The end cap 24 may be made from, forexample, nickel-plated steel or tin-plated steel. The end cap 24 may beelectrically connected to the current collector 20. The end cap 24 may,for example, make electrical connection to the current collector 20 bybeing welded to the current collector 20. The end cap 24 may alsoinclude one or more apertures, such as holes, for venting any gaspressure that may build up under the end cap 24 during a gassing eventwithin the battery 10, for example, during deep discharge or reversal ofthe battery 10 within a device, that may lead to rupturing of the vent.

The battery 10 including a cathode 12 including beta-delithiated layerednickel oxide may have an open-circuit voltage (OCV) that is measured involts. The battery 10 may have an OCV from about 1.70 V to about 1.85 V.The battery 10 may have an OCV, for example, at about 1.78 V.

Batteries including beta-delithiated layered nickel oxideelectrochemically active cathode materials of the present invention mayhave improved discharge performance for low, mid, and high draindischarge rates than, for example, batteries including high-oxidationstate transition metal oxide electrochemically active cathode materials.Batteries including beta-delithiated layered nickel oxideelectrochemically active cathode materials of the present invention mayhave lower closed circuit voltages than, for example, batteriesincluding high-oxidation state transition metal oxide electrochemicallyactive cathode materials. Batteries including beta-delithiated layerednickel oxide electrochemically active cathode materials of the presentinvention may have lower gas evolution than, for example, batteriesincluding high-oxidation state transition metal oxide electrochemicallyactive cathode materials. Batteries including beta-delithiated layerednickel oxide electrochemically active cathode materials of the presentinvention may have greater cathode structural integrity, continuity, andleakage characteristics than, for example, batteries includinghigh-oxidation state transition metal oxide electrochemically activecathode materials. The beta-delithiated layered nickel oxideelectrochemically active cathode materials of the present invention mayconsume less water, resulting in less cathode swelling and unfavorablewater balancing, when incorporated within a battery than, for example,high-oxidation state transition metal oxide electrochemically activecathode materials incorporated within a battery.

Referring to FIG. 2, the XRD patterns of several sample materials areshown. An exemplary XRD pattern of a beta-delithiated layered nickeloxide 110 (Li_(0.06)K_(0.12)NiO₂.0.53H₂O) of the present invention isincluded within FIG. 2. The exemplary XRD pattern of thebeta-delithiated layered nickel oxide 110 includes a first peak at about15.6°2θ (111); a second peak at about 21.9°2θ (112); a third peak atabout 37.3°2θ (113); a fourth peak at about 43.6°2θ(114); a fifth peakat about 59.9°2θ (115); and a sixth peak at about 65.8°2θ (116). Theexemplary XRD pattern of the beta-delithiated layered nickel oxide 110also includes a seventh peak at about 11.2°2θ (117); a eighth peak atabout 47.3°2θ (118); and a ninth peak at about 48.3°2θ (119).

Still referring to FIG. 2, an exemplary XRD pattern of gamma-nickeloxyhydroxide 120 (γ-NiOOH) is shown. The XRD pattern of gamma-nickeloxyhydroxide 120 includes a first peak at about 12.8°2θ (121); a secondpeak at about 25.5°2θ (122); a third peak at about 37.8°2θ (123); afourth peak at about 42.9°2θ (124); a fifth peak at about 66.3°2θ (125);and a sixth peak at about 67.7°2θ (126). The XRD pattern of thebeta-delithiated layered nickel oxide differs from the XRD pattern ofgamma-nickel oxyhydroxide. For example, the XRD pattern of thebeta-delithiated layered nickel oxide includes, inter alia, distinctpeaks within the XRD pattern at about 15.6°2θ (111); at about 21.9°2θ(112); and at about 59.9°2θ (115). The XRD pattern of gamma-nickeloxyhydroxide does not include such peaks. In addition, the XRD patternof the beta-delithiated layered nickel oxide includes, inter alia,distinct peaks within the XRD pattern at about 11.2°2θ (117); at about47.3°2θ (118); and at about 48.3°2θ (119). The XRD pattern ofgamma-nickel oxyhydroxide does not include such peaks.

Still referring to FIG. 2, an exemplary XRD pattern of analpha-delithiated layered nickel oxide 130 (Li_(0.06)NiO₂) is shown. Theexemplary XRD pattern of the alpha-delithiated layered nickel oxide 130includes a first peak at about 18.5°2θ (131); a second peak at about37.2°2θ (132); a third peak at about 38.8°2θ (133); a fourth peak atabout 44.9°2θ (134); a fifth peak at about 58.6°2θ (135); and a sixthpeak at about 64.1°2θ (136). The XRD pattern of the beta-delithiatedlayered nickel oxide differs from the XRD pattern of thealpha-delithiated layered nickel oxide. For example, the XRD pattern ofthe beta-delithiated layered nickel oxide includes, inter alia, distinctpeaks within the XRD pattern at about 15.6°2θ (111); at about 21.9°2θ(112); and at about 43.6°2θ (114). The XRD pattern of thealpha-delithiated layered nickel oxide does not include such a peak. Inaddition, the XRD pattern of the beta-delithiated layered nickel oxideincludes, inter alia, distinct peaks within the XRD pattern at about11.2°2θ (117). The XRD pattern of the alpha-delithiated layered nickeloxide does not include such a peak.

Still referring to FIG. 2, an exemplary XRD pattern of nickel oxide 140(NiO) is shown. The XRD pattern of nickel oxide 140 includes a firstpeak at about 37.2°2θ (141); a second peak at about 43.3°2θ (142); and athird peak at about 62.9°2θ (143). The XRD pattern of thebeta-delithiated layered nickel oxide differs from the XRD pattern ofnickel oxide. For example, the XRD pattern of the beta-delithiatedlayered nickel oxide includes, inter alia, distinct peaks within the XRDpattern at about 15.6°2θ (111); at about 21.9°2θ (112); at about 59.9°2θ(115); and at about 65.8°2θ (116). The XRD pattern of nickel oxide doesnot include such peaks. In addition, the XRD pattern of thebeta-delithiated layered nickel oxide includes, inter alia, distinctpeaks within the XRD pattern at about 11.2°2θ (117); at about 47.3°2θ(118); and at about 48.3°2θ (119). The XRD pattern of nickel oxide doesnot include such peaks.

Still referring to FIG. 2, an exemplary XRD pattern of beta-nickelhydroxide 150 (β-Ni(OH)₂) is shown. The XRD pattern of beta-nickelhydroxide 150 includes a first peak at about 19.2°2θ (151); a secondpeak at about 33.1°2θ (152); a third peak at about 38.5°2θ (153); afourth peak at about 52.2°2θ (154); a fifth peak at about 59.2°2θ (155);and a sixth peak at about 62.8°2θ (156). The XRD pattern of thebeta-delithiated layered nickel oxide differs from the XRD pattern ofbeta-nickel hydroxide. For example, the XRD pattern of thebeta-delithiated layered nickel oxide includes, inter alia, distinctpeaks within the XRD pattern at about 15.6°2θ (111); at about 21.9°2θ(112); at about 43.6°2θ (114); and at about 65.8°2θ (116). The XRDpattern of beta-nickel hydroxide does not include such peaks. Inaddition, the XRD pattern of the beta-delithiated layered nickel oxideincludes, inter alia, distinct peaks within the XRD pattern at about11.2°2θ (117); at about 47.3°2θ (118); and at about 48.3°2θ (119). TheXRD pattern of beta-nickel hydroxide does not include such peaks.

Still referring to FIG. 2, an exemplary XRD pattern of beta-nickeloxyhydroxide 160 (β-NiOOH) is shown. The XRD pattern of beta-nickeloxyhydroxide 160 includes a first peak at about 19.1°2θ (161) and asecond peak at about 37.9°2θ (162). The XRD pattern of thebeta-delithiated layered nickel oxide differs from the XRD pattern ofbeta-nickel oxyhydroxide. For example, the XRD pattern of thebeta-delithiated layered nickel oxide includes, inter alia, distinctpeaks within the XRD pattern at about 15.6°2θ (111); at about 21.9°2θ(112); at about 43.6°2θ (114); at about 59.9°2θ (115); and at about65.8°2θ (116). The XRD pattern of beta-nickel oxyhydroxide does notinclude such peaks. In addition, the XRD pattern of the beta-delithiatedlayered nickel oxide includes, inter alia, distinct peaks within the XRDpattern at about 11.2°2θ (117); at about 47.3°2θ (118); and at about48.3°2θ (119). The XRD pattern of beta-nickel oxyhydroxide does notinclude such peaks.

Still referring to FIG. 2, an exemplary XRD pattern of potassiumhydroxide 170 (KOH). The XRD pattern of potassium hydroxide 170 includesa first peak at about 22.1°2θ (171); a second peak at about 28.4°2θ(172); a third peak at about 30.5°2θ (173); a fourth peak at about33.3°2θ (174); a fifth peak at about 39.1°2θ (175); and a sixth peak atabout 45.8°2θ (176). The XRD pattern of the beta-delithiated layerednickel oxide differs from the XRD pattern of potassium hydroxide. Forexample, the XRD pattern of the beta-delithiated layered nickel oxideincludes, inter alia, distinct peaks within the XRD pattern at about15.6°2θ (111); at about 37.3°2θ (113); at about 43.6°2θ (114); at about59.9°2θ (115); and at about 65.8°2θ (116). The XRD pattern of potassiumhydroxide does not include such peaks. In addition, the XRD pattern ofthe beta-delithiated layered nickel oxide includes, inter alia, distinctpeaks within the XRD pattern at about 11.2°2θ (117). The XRD pattern ofpotassium hydroxide does not include such peaks.

Still referring to FIG. 2, the XRD patterns of the beta-delithiatedlayered nickel oxide 110; the alpha-delithiated layered nickel oxide130; nickel oxide 140; beta-nickel hydroxide 150; and potassiumhydroxide 170 include a peak at about 28.5°2θ (101) that is indicativeof the NIST 640d silicon standard. The silicon standard is used for 2θdiffraction angle calibration.

Referring to FIG. 3, a battery 310 including a label 320 that has anindicator, or tester, 330 incorporated within the label 320 todetermine, for example, the voltage, capacity, state of charge, and/orpower of the battery 310 is shown. The label 320 may be a laminatedmulti-layer film with a transparent or translucent layer bearing thelabel graphics and text. The label 320 may be made from polyvinylchloride (PVC), polyethylene terephthalate (PET), and other similarpolymer materials. The tester 330 may include, for example, athermochromic or an electrochromic indicator. In a thermochromic batterytester, the indicator may be placed in electrical contact with thehousing and the end cap the battery 310. The consumer activates theindicator by manually depressing a switch located within an electricalcircuit included within the tester 330. Once the switch is depressed,the consumer has connected an anode of the battery 310, via the end cap,to a cathode of the battery 310, via the housing, through thethermochromic tester. The thermochromic tester may include a silverconductor that has a variable width so that the resistance of theconductor also varies along its length. The current generates heat thatchanges the color of a thermochromic ink display that is over the silverconductor as the current travels through the silver conductor. Thetester 330 may be arranged as a gauge to indicate, for example, therelative capacity of the battery 310. The higher the current the moreheat is generated and the more the gauge will change to indicate thatthe battery 310 is good.

Experimental Testing Elemental Analysis Via ICP-AE

Elemental analysis via ICP-AE is completed on a sample ofelectrochemically active material to determine the elemental content ofthe sample material. ICP-AE analysis is completed using the HORIBAScientific Ultima 2 ICP spectrometer. ICP-AE analysis is completed byplacing a sample solution within the spectrometer. The sample solutionis prepared in a manner that is dependent upon the element(s) that aredesired to be analyzed.

For elemental analysis, a first solution is made by adding approximately0.15 grams of the sample material to about 20 mL of an eight normal (8N)solution of nitric acid (HNO₃). The first solution is heated, at about210° C., until almost all the liquid is evaporated off. The firstsolution is then allowed to cool to between about 100° C. to about 150°C. A second solution is formed by adding about 10 mL of concentratedhydrochloric acid (HCl) to the first solution after the first solutionhas cooled. The second solution is heated, at about 210° C., untilalmost all the liquid is evaporated off. The second solution is thenallowed to cool. A third solution is formed by adding about 10 mL ofconcentrated HCl to the second solution after the second solution hascooled to between about 100° C. to about 150° C. The third solution isheated, at about 210° C., until almost all liquid is evaporated off. Thethird solution is then placed into an oven at about 110° C. for onehour. After storage within the oven, the third solution is allowed tocool. A fourth solution is formed by adding 5 mL concentrated HCl to thethird solution. The fourth solution is heated, to about 210° C., untilthe sample material is dissolved within the fourth solution. The fourthsolution is allowed to cool. A fifth solution is formed by transferringthe fourth solution to a 100 mL volumetric flask and adding distilledwater, up to the 100 mL graduation mark of the volumetric flask, to thefourth solution. The fifth solution is used for elemental analysis oflithium (Li), potassium (K), and rubidium (Rb) using the ICP-AEspectrometer. A sixth solution is formed by transferring one mL of thefifth solution into a 50 mL centrifuge tube; adding about 2.5 mL ofconcentrated HCl to the centrifuge tube; adding distilled water to thecentrifuge tube so that the total weight of the sixth solution is 50grams; and mixing the components of the centrifuge tube. The sixthsolution is used for elemental analysis of nickel (Ni) using the ICP-AEspectrometer.

ICP-AE analysis of the beta-delithiated layered nickel oxide isperformed at various wavelengths specific to potassium (K), lithium(Li), nickel (Ni), and rubidium (Rb). For example, the wavelength (λ)for analysis of potassium (K) within a beta-delithiated layered nickeloxide may be set at about 766 nm. For example, the wavelength (λ) foranalysis of lithium (Li) within a beta-delithiated layered nickel oxidemay be set at about 610 nm. For example, the wavelength (λ) for analysisof nickel (Ni) within a beta-delithiated layered nickel oxide may be setat about 231 nm. For example, the wavelength (λ) for analysis ofrubidium (Rb) within a beta-delithiated layered nickel oxide may be setat about 780 nm.

Table 1 below includes the elemental analysis via ICP-AE results for thealpha-delithiated layered nickel oxide (Material A) and thebeta-delithiated layered nickel oxide (Material B). The weight percentof lithium (Li), nickel (Ni), and potassium (K) within the samplematerial is reported. The elemental analysis via ICP-AE data is used todetermine the chemical composition of Material A and Material B. Theelemental analysis via ICP-AE is also used to confirm that Material Aand Material B do not have undesirable side products or decompositionproducts within their respective chemical compositions.

Water Content Via Thermogravimetric Analysis (TGA)

Water content via TGA is completed on a sample of electrochemicallyactive material to determine the absorbed/adsorbed water, thecrystalline water, and total water content within the sample material.TGA analysis is completed using the TA Instruments Q5000 analyzer.

TGA analysis is conducted by placing about 34 mg of sample onto the TGAsample holder. The sample material is heated at a rate of 5° C./min to atemperature of about 800° C. The heating of the sample occurs in thepresence of nitrogen that is flowing at a rate of, for example, about 25mL/min. The sample weight is measured as a function of time andtemperature.

Table 1 includes the water content that is measured via TGA for thealpha-delithiated layered nickel oxide (Material A) and thebeta-delithiated layered nickel oxide (Material B). The water contentthat is measured via TGA is used to determine the lattice water presentin the chemical compositions of Material A and Material B. The watercontent that is measured via TGA is also used to determine the wateradsorbed to the surface of Material A and Material B and to confirm thatno excess water is present in the respective materials.

Qualitative Gas Evolution Rate (GER) Analysis

Qualitative gas generation rate (GER) analysis is completed on a sampleof electrochemically active material to qualitatively determine the rateof gas evolution. The qualitative GER analysis is completed throughvisual observation. The qualitative GER analysis includes placing aboutone gram of sample material in a Petri dish and adding about 0.5 gramsof nine normal (9N) aqueous potassium hydroxide electrolyte to thesample material within the Petri dish. The qualitative GER is thenvisually observed and recorded.

Table 1 includes the qualitative GER results for the alpha-delithiatedlayered nickel oxide (Material A) and the beta-delithiated layerednickel oxide (Material B). The alpha-delithiated layered nickel oxide(Material A) exhibits a high qualitative GER. The beta-delithiatedlayered nickel oxide (Material B) exhibits a low qualitative GER.

Quantitative Gas Evolution Rate (GER) Analysis

Quantitative gas evolution rate (GER) analysis is completed on a sampleof electrochemically active material to quantitatively determine therate of gas evolution. The quantitative GER analysis is completed usingthe Valcom Series 27A pressure sensor attached to the cap of a sealable,100 mL glass jar. The Agilent 34970A Data acquisition unit is attachedto the pressure sensor. A mixture of about 2.5 grams of sample materialand about 1.5 grams of nine normal (9N) aqueous potassium hydroxideelectrolyte is placed within the glass jar. The glass jar is then sealedwith the cap. The sealed glass jar is then placed into an oven at atemperature of about 40° C. The pressure of any gas that is generatedover time by the sample material in contact with the electrolyte isrecorded by the Agilent data logger.

Table 1 includes the quantitative GER results for the alpha-delithiatedlayered nickel oxide (Material A) and the beta-delithiated layerednickel oxide (Material B). The beta-delithiated layered nickel oxide(Material B) initially produces gas. After approximately 20 hours ofmeasurement, Material B generates about 65 mBar of gas. Afterapproximately 40 hours of measurement, Material B generates about 69mBar of gas. After approximately 80 hours of measurement, Material Bgenerates about 74 mBar of gas.

The alpha-delithiated layered nickel oxide (Material A) initiallyproduces a greater quantity of gas, and at a faster rate, than MaterialB. After approximately 20 hours of measurement, Material A generatesabout 137 mBar of gas. After approximately 40 hours of measurement,Material B generates about 150 mBar of gas. After approximately 80 hoursof measurement, Material B generates about 169 mBar of gas. The gas thatis generated by Material A, for each measurement point, is greater thantwo times the amount of gas that is generated by Material B at the samemeasurement point.

Stability Determination Via Isothermal Microcalorimetry (IMC) Analysis

Stability determination via IMC is performed on a sample ofelectrochemically active material to determine the amount, and rate, ofheat that is generated by the sample material in contact with anelectrolyte. The stability determination is completed using the TAInstruments TAM III isothermal microcalorimeter. A mixture is preparedby adding about 1.5 grams of nine normal (9N) aqueous potassiumhydroxide electrolyte to about 2.5 grams of the sample material within aglass beaker. About one gram of the mixture is transferred into a 1.5 mLplastic vial. The plastic vial containing the mixture is placed into aTA Instruments 4 mL glass ampoule. The glass ampoule is then sealed andis placed into the isothermal microcalorimeter at a temperature of about40° C. The heat that is generated by the sample material versus time isthen measured and is recorded.

Table 1 includes the stability determination via IMC results for thealpha-delithiated layered nickel oxide (Material A) and thebeta-delithiated layered nickel oxide (Material B). Both Material A andMaterial B initially generate heat, respectively, about 7×10⁻³ W/g andabout 1×10⁻³ W/g respectively. The heat being produced by Material Astabilizes, and remains relatively constant, at about 1×10⁻³ W/g afterabout two hours of measurement. At this same point in time, the heatbeing produced by Material B, however, has decreased to about 7×10⁻⁵W/g. The heat being produced by Material A, about 1×10⁻³ W/g, andMaterial B, about 6×10⁻⁵ W/g, remains relatively constant after aboutone day of measurement. The heat being produced by Material A, about4×10⁻⁵ W/g, and Material B, about 2×10⁻⁵ W/g, decreases after aboutthree days of measurement.

Material B, after an initial spike in heat generation, generates lessheat while in the presence of nine normal (9N) aqueous potassiumhydroxide electrolyte than Material A. Material B is thus more stablethan Material A when in the presence of 9N aqueous potassium hydroxideelectrolyte. The stability measurements confirm the relative reactivityof Material A and Material B seen in the qualitative and quantitativeGER experiments discussed above.

TABLE 1 ICP-AE, TGA, GER, AND IMC DATA FOR MATERIAL A AND MATERIAL B.MATERIAL A MATERIAL B FEATURE (Li_(0.06)NiO₂)(Li_(0.06)K_(0.12)NiO₂•0.53H₂O) ICP-AE Lithium (weight percent) 0.55%0.49% Nickel (weight percent) 72.0% 65.2% Potassium (weight percent) 05.2% TGA Absorbed/Adsorbed Water — 4 (weight percent) Crystalline Water(weigth — 10 percent) Total Water (weight — 14 percent) Qualitative GERHigh Low Quantitative GER Gas Pressure @ 20 hrs 137 65 (mBar) GasPressure @ 40 hrs 150 69 (mBar) Gas Pressure @ 80 hrs 160 74 (mBar) IMCInitial (W/g) 7 × 10⁻³ 1 × 10⁻³ 2 hours (W/g) 1 × 10⁻³ 7 × 10⁻⁵ 1 day(W/g) 1 × 10⁻³ 6 × 10⁻⁵ 3 days (W/g) 4 × 10⁻⁵ 2 × 10⁻⁵

Powder X-Ray Diffraction Analysis

Powder X-ray diffraction (XRD) analysis is performed on a crystallinepowder sample to determine the characteristic XRD diffraction pattern ofthe crystalline powder sample. XRD analysis is completed using theBruker D-8 Advance X-ray diffractometer. XRD analysis is performed on abeta-delithiated layered nickel oxide as well as several comparativesamples. About one gram to about two grams of the sample material isplaced within the Bruker sample holder. The sample holder including thesample material is then placed into the rotating sample stage of theX-ray diffractometer and the sample material is then irradiated by theCuK_(α) X-ray source of the diffractometer. The X-rays that arediffracted are measured by a Sol-x detector, available from BalticScientific Instruments (Riga, Latvia). The XRD pattern of each sample isthen collected using a 0.02° step size at 2 seconds/step from 10°2θ to80°2θ using Diffrac-plus software supplied by Bruker Corporation. TheXRD pattern for the sample material is then analyzed using EVA and Topasdata analysis software packages, both available from Bruker Corporation.The XRD pattern of the sample material is compared to reference XRDpatterns that are measured for known materials.

Table 2 summarizes the sample and known materials analyzed and thecharacteristic peaks within the XRD pattern of each of the materials.

TABLE 2 SUMMARY OF THE MAIN DIFFRACTION PEAKS IN THE XRD PATTERNS OF THESAMPLE AND KNOWN MATERIALS. FIRST SECOND THIRD FOURTH FIFTH SIXTH SAMPLEMATERIAL PEAK PEAK PEAK PEAK PEAK PEAK β-Delithiated Layered 15.6 21.937.3 43.6 59.9 65.5 Nickel Oxide (Li0.06K0.12NiO2•0.53H2O) α-DelithiatedLayered 18.5 37.2 38.8 44.9 58.6 64.1 Nickel Oxide (Li0.06NiO2) β-NickelOxyhydroxide 18.35 37.27 — — — — γ-Nickel Oxyhydroxide 12.8 25.6 37.943.2 66.3 67.7 Nickel Oxide 37.2 43.3 62.9 — — — β-Nickel Hydroxide 19.233.1 38.5 52.2 59.2 62.8 Potassium Hydroxide 22.1 28.4 30.5 33.3 39.145.8

Performance Testing of Assembled AAA Alkaline Primary Batteries

An exemplary AAA battery, referred to as Battery A in Table 3 below, isassembled. Battery A includes an anode, a cathode, a separator, and anaqueous alkaline electrolyte within a cylindrical housing. The anodeincludes an anode slurry containing 1.96 grams of zinc; 0.875 grams of apotassium hydroxide alkaline electrolyte with about 30% KOH by weightand 2% ZnO by weight dissolved in water; 0.02 grams of polyacrylic acidgellant; and 0.01 grams of corrosion inhibitor. The cathode includes ablend of alpha-delithiated layered nickel oxide, graphite, and potassiumhydroxide aqueous electrolyte solution. The cathode has a loading of3.35 grams of alpha-delithiated layered nickel oxide, a loading of 0.40grams Timcal BNC-30 graphite, and 0.21 grams of electrolyte. Theseparator is interposed between the anode and cathode. The anode,cathode, and separator are inserted into the cylindrical housing. Thehousing is then sealed to complete the battery assembly process. BatteryA then undergoes aging and performance testing as is described below.

An experimental AAA battery, referred to as Battery B in Table 3 below,is assembled. Battery B includes an anode, a cathode, a separator, andan aqueous alkaline electrolyte within a cylindrical housing. The anodeincludes an anode slurry containing 1.96 grams of zinc; 0.875 grams of apotassium hydroxide alkaline electrolyte with about 30% KOH by weightand 2% ZnO by weight dissolved in water; 0.02 grams of polyacrylic acidgellant; and 0.01 grams of corrosion inhibitor. The cathode includes ablend of beta-delithiated layered nickel oxide, graphite, and potassiumhydroxide aqueous electrolyte solution. The cathode includes a loadingof 3.35 grams of a beta-delithiated layered nickel oxide, a loading of0.40 grams Timcal BNC-30 graphite, and 0.21 grams of electrolyte. Aseparator is interposed between the anode and cathode. The anode,cathode, and separator are inserted into the cylindrical housing. Thehousing is then sealed to complete the battery assembly process. BatteryB then undergoes aging and performance testing as is described below.

TABLE 3 THE DESIGN FEATURES OF AAA BATTERY A AND BATTERY B. FEATUREBATTERY A BATTERY B Anode Zinc Weight 1.96 g 1.96 g Gelling Agent Weight0.02 g 0.02 g Corrosion Inhibitor Weight 0.01 g 0.01 g Cathode ActiveWeight 3.35 g 3.35 g (Li_(0.06)NiO₂) (Li_(0.06)K_(0.12)NiO₂•0.53H₂O)Graphite Weight 0.40 g 0.40 g Complete Cell Total KOH Weight 0.56 g 0.56g Total Water Weight 1.19 g 1.19 g Total ZnO Weight 0.03 g 0.03 g

Performance testing includes discharge performance testing that may bereferred to as the Power Signature Test. The Power Signature Testprotocol includes sequentially applying a high rate, a medium rate, anda low rate discharge regime to the battery, with recovery, or restperiods in between each of the discharge regimes. The high ratedischarge regime is first applied to the battery. The high ratedischarge regime includes applying a constant power drain of 0.5 wattsto the battery until the cutoff voltage of 0.9 volts is reached. Thebattery is then allowed to recover for a period of 4 hours. The mediumrate discharge regime is then applied to the battery. The medium ratedischarge regime includes applying a constant power drain of 0.125 wattsto the battery until the cutoff voltage of 0.9 volts is reached. Thebattery is then allowed to recover for a period of 4 hours. The low ratedischarge regime is then applied to the battery. The low rate dischargeregime includes applying a constant power drain of 0.025 watts to thebattery until the cutoff voltage of 0.9 volts is reached. The measuredcapacity of the battery, in ampere hours (Ah), is reported for eachindividual discharge regime. In addition, the cumulative measuredcapacity for the battery for all the discharge regimes, in ampere hours(Ah), is also reported.

Performance testing includes discharge performance testing that may bereferred to as the 30 Milliampere Continuous Discharge Test (30 mAContinuous). The 30 mA Continuous protocol includes applying a constantcurrent drain of 30 mA to the battery until the cutoff voltage of 0.9volts is reached. The measured total capacity of the battery is reportedin ampere hours (Ah). The 30 mA Continuous Discharge Test is a low ratedischarge test.

Prior to performance testing, the battery is aged for four days at about20° C. After four days of aging, the Open Circuit Voltage (OCV) of thebattery is measured. The OCV of the battery is measured by placing, forexample, a voltmeter across the positive and negative terminals of thebattery. The measured open circuit voltage (V) of the battery isreported. The OCV test does not consume any capacity from the battery.

After four days of aging, the Short Circuit Current (SCC) of the batteryis measured. The SCC protocol includes applying a constant current ofsix amperes (Amps) for a period of 0.1 seconds to the battery. Thevoltage of the battery is measured while under the drain of six Amps andis reported. The battery would have a measured voltage of zero (0) voltsif the battery is completely short circuited. The current at which thebattery would short circuit is calculated by extrapolating the linebetween the coordinates of the measured OCV and the measured voltageunder drain to the intercept of the x-axis on an x,y plot of currentversus voltage. The measured OCV has an (x,y) coordinate of (0 Amp,OCV). The measured voltage under drain has an (x,y) coordinate of (6Amp, Load Voltage). The SSC test does not consume significant capacityfrom the battery due to the extremely short duration of the test. TheSSC is calculated by the following formula:

SSC (Amps)=[(OCV·6 Amp)/(OCV−Load Voltage)]

Performance Testing Results

Battery A and Battery B undergo OCV, SSC, Power Signature, and 30 mAContinuous performance testing. Table 4 below summarizes the performancetesting results. The Difference column of Table 4 includes thepercentage difference in performance for Battery B with respect toBattery A.

Battery B that includes beta-delithiated layered nickel oxide providesimproved overall performance when compared with Battery A that includesalpha-delithiated layered nickel oxide. The OCV of Battery B is slightlyreduced when compared with Battery A. The lower OCV of Battery B reducesthe likelihood of damage when Battery B is incorporated in an electricaldevice than the higher OCV of Battery A. The SSC of Battery B issignificantly higher than Battery A. The higher SSC of Battery B isindicative of a greater ability to carry higher discharge currents thanBattery A. The capacity of Battery B under the high discharge rate andmedium discharge rate regimes of the Power Signature Test issignificantly higher than Battery A. The higher discharge capacity ofBattery B is indicative of a greater ability to provide improvedperformance under these discharge conditions than Battery A. Thecapacity of Battery B under the low rate discharge regime of the PowerSignature Test is lower than Battery A. The lower discharge capacity ofBattery B is due to the greater consumption of capacity under the highand the medium discharge regimes of the Power Signature Test thanBattery A. The cumulative discharge capacity of Battery B is greaterthan Battery A. The greater cumulative discharge capacity of Battery Bis indicative of a higher total deliverable capacity than Battery A. Thecapacity of Battery B under the 30 mA Continuous Test is also higherthan Battery A. The higher discharge capacity of Battery B is indicativeof a greater ability to provide improved performance under low ratedischarge conditions than Battery A.

TABLE 4 PERFORMANCE TESTING RESULTS AND COMPARISONS FOR BATTERY A ANDBATTERY B. % DIFFER- TEST PROTOCOL BATTERY A BATTERY B ENCE OCV (V)1.827 1.791  −3% SSC (Amps) 12.3 16.2 +32% Power Signature: 0.375 0.75+100%  0.5 Watt Capacity (Ah) Power Signature: 0.275 0.375 +36% 0.125Watt Capacity (Ah) Power Signature: 0.425 0.035 −92% 0.025 Watt Capacity(Ah) Power Signature: 1.075 1.16  +8% Total Capacity (Ah) 30 mAContinuous 0.95 1.16 +22% (Ah)

Performance Testing of Assembled AA Alkaline Primary Batteries

An exemplary AA battery, referred to as Battery C in Table 5 below, isassembled. Battery C includes an anode, a cathode, a separator, and anaqueous alkaline electrolyte within a cylindrical housing. The anodeincludes an anode slurry containing 5.04 grams of zinc; 2.32 grams of apotassium hydroxide alkaline electrolyte with about 28% KOH by weightand 1.8% ZnO by weight dissolved in water; 0.04 grams of polyacrylicacid gellant; and 0.01 grams of corrosion inhibitor. The cathodeincludes a blend of alpha-delithiated layered nickel oxide, graphite,and potassium hydroxide aqueous electrolyte solution. The cathodeincludes a loading of 8.99 grams of alpha-delithiated layered nickeloxide, a loading of 0.92 grams Timcal BNC-30 graphite, and 0.49 grams ofelectrolyte. A separator is interposed between the anode and cathode.The anode, cathode, and separator are inserted into a cylindricalhousing. The housing is then sealed to complete the battery assemblyprocess. Battery C then undergoes aging and performance testing as isdescribed below.

An experimental AA battery, referred to as Battery D in Table 5 below,is assembled. Battery D includes an anode, a cathode, a separator, andan electrolyte within a cylindrical housing. The anode includes an anodeslurry containing 4.83 grams of zinc; 2.287 grams of a potassiumhydroxide alkaline electrolyte with about 28% KOH by weight and 1.8% byZnO weight dissolved in water; 0.04 grams of polyacrylic acid gellant;and 0.01 grams of corrosion inhibitor. The cathode includes a blend ofbeta-delithiated layered nickel oxide, graphite, and potassium hydroxideaqueous electrolyte solution. The cathode includes a loading of 8.99grams of a beta-delithiated layered nickel oxide, a loading of 0.92grams Timcal BNC-30 graphite, and 0.49 grams of electrolyte. A separatoris interposed between the anode and cathode. The anode, cathode, andseparator are inserted into a cylindrical housing. The housing is thensealed to complete the battery assembly process. Battery D thenundergoes aging and performance testing as is described below.

TABLE 5 THE DESIGN FEATURES OF AA BATTERY C AND BATTERY D. FEATUREBATTERY C BATTERY D Anode Zinc Weight 5.04 g 4.83 g Gelling Agent Weight0.04 g 0.04 g Corrosion Inhibitor Weight 0.01 g 0.01 g Cathode ActiveWeight 8.99 g 8.99 g (Li_(0.06)NiO₂) (Li_(0.06)K_(0.12)NiO₂•0.53H₂O)Graphite Weight 0.92 g 0.92 g Complete Cell Total KOH Weight 1.10 g 1.07g Total Water Weight 2.87 g 2.80 g Total ZnO Weight 0.07 g 0.07 g

Performance testing includes OCV, SSC, and 30 mA Continuous testingaccording to the protocols that are described within the sectionPerformance Testing of Assembled AAA Alkaline Primary Batteries above.The battery is aged for four days at about 20° C. prior to performancetesting.

Performance Testing Results

Battery C and Battery D undergo OCV, SSC, and 30 mA Continuousperformance testing. Table 6 below summarizes the performance testingresults. The % Difference column of Table 6 includes the percentagedifference in performance for Battery D with respect to Battery C.

Battery D that includes beta-delithiated layered nickel oxide providesimproved overall performance when compared with Battery C that includesalpha-delithiated layered nickel oxide. The OCV of Battery D is slightlyreduced when compared with Battery C. The lower OCV of Battery D reducesthe likelihood of damage when Battery D is incorporated in an electricaldevice than the higher OCV of Battery C. The SSC of Battery D issignificantly higher than Battery C. The higher SSC of Battery D isindicative of a greater ability to carry higher discharge currents thanBattery C. The capacity of Battery D under the 30 mA Continuous Test isalso higher than Battery C. The higher discharge capacity of Battery Dis indicative of a greater ability to provide improved performance underlow rate discharge conditions than Battery C.

TABLE 6 PERFORMANCE TESTING RESULTS AND COMPARISONS FOR BATTERY C ANDBATTERY D. % DIFFER- TEST PROTOCOL BATTERY C BATTERY D ENCE OCV (V) 1.811.79  −10% SSC (Amps) 23.3 24.7  +6% 30 mA Continuous 1.23 3.1 +152%(Ah)

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. An electrochemically active cathode material comprising abeta-delithiated layered nickel oxide, the beta-delithiated layerednickel oxide having an X-ray diffraction pattern comprising a first peakfrom about 14.9°2θ to about 16.0°2θ; a second peak from about 21.3°2θ toabout 22.7°2θ; a third peak from about 37.1°2θ to about 37.4°2θ; afourth peak from about 43.2°2θ to about 44.0°2θ; a fifth peak from about59.6°2θ to about 60.6°2θ; and a sixth peak from about 65.4°2θ to about65.9°2θ.